非晶合金Fe_(3)Ni_(3)的轨道杂化及成键性质研究  

Orbital hybridization and bonding properties of amorphous alloy Fe_(3)Ni_(3)

作　　者：郑新喜 方志刚[1] 曾鑫渔 侯欠欠 刘立娥 ZHENG Xinxi;FANG Zhigang;ZENG Xinyu;HOU Qianqian;LIU Li’e(School of Chemical Engineering,University of Science and Technology Liaoning,Anshan 114051,Liaoning,China)

机构地区：[1]辽宁科技大学化学工程学院,辽宁鞍山114051

出　　处：《天然气化工—C1化学与化工》2022年第6期91-96,共6页Natural Gas Chemical Industry

基　　金：国家自然科学基金(51634004);国家级大学生创新创业训练计划(202110146027,202110146009,202110146016);辽宁省大学生创新创业训练计划(202110146056,202110146049,202110146030)。

摘　　要：为探究团簇Fe_(3)Ni_(3)优化构型内的轨道杂化及成键情况,在密度泛函理论中的B3LYP/Lanl2dz水平下,利用Gaussian软件对构型进行全参数优化计算后,得到9种稳定的优化构型,发现三重态构型均较单重态构型稳定。进一步分析各优化构型的态密度发现,团簇Fe_(3)Ni_(3)各优化构型内部主要存在4s-4s、4p-4p、4p-3d与3d-3d 4种轨道杂化方式,其中4s-4s轨道杂化贡献最弱,3d-3d轨道杂化的贡献最强。从键长、键级与键级贡献比3个角度探究成键性质发现,Fe—Fe键与Fe—Ni键的存在对构型稳定性均具有促进作用,其中三重态中Fe—Ni键起主要贡献作用,而单重态中Fe—Fe键贡献作用最大,说明自旋多重度对构型内成键具有选择性,进而影响其稳定性。In order to explore the orbital hybridization and bonding in the optimized configuration of amorphous alloy Fe_(3)Ni_(3),under the B3LYP/Lanl2dz level in density functional theory,the Gaussian software was used to optimize the configuration with all parameters,and nine stable configurations were obtained.It is found that the triplet configuration is more stable than the singlet configuration.Further analysis of the state density of each optimized configuration shows that there are four orbital hybridization modes of 4s-4s,4p-4p,4p-3d and 3d-3d in each optimized configuration of the Fe_(3)Ni_(3) cluster,among which the contribution of 4s-4s orbital hybridization is the weakest and that of 3d-3d orbital hybridization is the strongest.From three aspects of bond length,bond level and bond level contribution ratio,it is found that the existence of Fe—Fe bond and Fe—Ni bond both promotes the configuration stability,and the Fe—Ni bond in the triplet state plays a major role,and the Fe—Fe bond in the singlet state contributes the most,which indicates that spin multiplicity is selective for intra-configurational bonding,and then affects its stability.

关 键 词：非晶合金Fe_(3)Ni_(3) 密度泛函理论 态密度 轨道杂化 成键 

分 类 号：TQ426.1[化学工程] O641.12[理学—物理化学]